厌氧发酵技术处理餐厨垃圾产沼气的研究
摘要
随着全球人口的增长，餐厨垃圾的排放量逐渐增大，大量的餐厨垃圾一方面给世界各国带来了严重的环境污染，另一方面导致了大量生物质能的浪费。传统的餐厨垃圾处理方法（如焚烧、填埋等）虽然能将餐厨垃圾处理，但会产生二次污染，不利于环境保护。作为一种绿色环保的处理工艺，厌氧发酵技术不但可以通过微生物将餐厨垃圾降解，还可以回收餐厨垃圾中的生物质能并将其转化为能源气体——甲烷。本文进行了厌氧发酵技术处理餐厨垃圾产沼气的研究，在优化小试发酵的基础上进行了中试水平的实验；采用了餐厨垃圾固液分离双发酵工艺，克服了高浓度盐分和油脂对厌氧发酵的抑制；将餐厨垃圾与牛粪进行混合发酵，使原料中的营养元素更为均衡，提高了厌氧发酵效率。主要工作如下：
1、由于批式发酵对餐厨垃圾的处理能力较低，本文在批式发酵的基础上，重点考察了序批式厌氧发酵，优化了序批式发酵的操作条件，并建立了序批式发酵过程中一个周期内的甲烷产气模型。批式发酵结果表明，厌氧发酵最佳的总固体（TS）浓度为5.6%，对应的沼气产率可达888mL/g-VS。序批式发酵的最佳进料负荷和保留时间分别为8g-VS/L和2d，对应的甲烷产率和化学需氧量（COD）去除率分别为436mL/g-VS和93.3%。在序批式发酵的一个进料周期内，甲烷的产气规律符合两个模型：有机酸积累时，为零级模型；有机酸无积累时，为一级模型。另外，研究了餐厨垃圾中各主要组分（淀粉、蛋白质和脂肪）单独厌氧发酵时的产气规律，建立了淀粉、蛋白质和脂肪的产气模型。研究结果表明，淀粉单独发酵时，产气规律符合slogistic模型，第1d为水解阶段，为限速步骤，沼气主要在第2d内产生，平均沼气产率为448mL/g-VS。蛋白质和脂肪单独发酵时的产气规律均符合零级模型，蛋白质的代谢速率较快，发酵在1d内完成；而脂肪的代谢速率较慢，发酵需要14d完成。混合发酵时，脂肪对淀粉和蛋白质的降解有抑制作用；在无脂肪存在的条件下，淀粉和蛋白质混合发酵的沼气产率比模型预测值高。
2、为了避免高浓度盐分和油脂对厌氧发酵的影响，研究了双发酵系统处理餐厨垃圾的工艺，即将餐厨垃圾的固液分离分别发酵，同时将油脂去除。批式发酵实验表明，固液分离后的固相和液相的产气速率和甲烷产率均比原餐厨的产气速率高，固相、液相和原餐厨对应的甲烷产率分别为643、659和581mL/g-VS。序批式发酵实验结果表明，固相、液相和原餐厨的最佳负荷率分别为9、4、7g-VS/L/d，在此条件下，固相、液相和原餐厨的甲烷产率分别为540、390、405mL/g-VS。基于1kg-VS原餐厨计，甲烷在双系统和单系统中的总产量分别为405L和460L，这说明甲烷的总产量在固液分离双系统中提高了13.6%。固相中的最佳C/N比、高浓度的微量元素和低浓度的油脂是双系统中沼气产量提高的原因。
3、为了平衡餐厨垃圾中的营养元素，进一步提高厌氧发酵效率，选用了牛粪作为餐厨垃圾的混合物，考察了餐厨垃圾与牛粪混合发酵性能。批式实验结果表明，当餐厨垃圾与牛粪的比例（FW/CM）为2：1时，厌氧发酵的甲烷产率最高，此配比下的批式发酵实验中，餐厨垃圾负荷为8g-VS/L时，混合发酵比餐厨垃圾单独发酵时的甲烷产率提高了41.1%，对应的甲烷的产率为388mL/g-VS。牛粪的加入提高了系统的缓冲能力，在没有pH调控的情况下，厌氧发酵能够在48g-VS/L的高负荷下稳定运行。利用响应面技术对甲烷产率进行了优化分析，结果表明，当餐厨垃圾的负荷为10g-VS/L/d时，混合体系的甲烷产率提高了55.2%，对应的甲烷产率为317mL/g-VS。较适宜的C/N、牛粪中丰富的微量元素和更强的油脂去除能力是混合发酵中沼气和甲烷产量提高的主要原因。
4、为了进一步提高厌氧发酵水平，本文对厌氧发酵罐进行了放大，分别考察了20L、30L和300L发酵罐的厌氧发酵。发酵稳定时，20L发酵罐的沼气和甲烷的产率分别为744mL/g-VS和467mL/g-VS，对应废水的COD值在5-6g/L之间，总氮和总硫的含量分别在400mg/L和10mg/L以下。30L发酵罐序批式发酵时的最佳的搅拌转速为100r/min，在此转速下发酵罐内部的大部分发酵液处于流动状态，平均流速为0.082m/s，既可以形成有效的传质，又可以形成致密性较好的颗粒污泥。300L发酵罐最佳的餐厨垃圾负荷为6g-VS/L/d，对应的平均沼气产率和废水COD分别为680mL/g-VS和4g/L。
The discharge of food waste (FW) is increasing due to the populationgrowth of the world. Large amount of FW, on the one hand, has caused severeenvironmental pollution in many countries. On the other hand, lots ofbio-energy in FW was wasted. The traditional disposal methods (e.g., aniamalfeed, incineration and landfill) could not meet the current demand ofenvironmental protection. As a green process, anaerobic digestion (AD) couldnot only dispose large amount of FW effectively, but also transform thebio-energy in organic waste into biogas. Biogas production from AD of FWwas investigated in this present paper. Pilot-scale anaerobic digestion wascarried out based on the operation condition of lab-scale anaerobic digestion.Anaerobic digestion in a dual solid-liquid (ADSL) system was applied toovercome the inhibition from higher concentration of salts and lipids.Moreover, to balance the nutrient elements of FW and enhance AD efficiency,cattle manure (CM) was applied as a co-substrate for AD of food waste. Themain contents are as follows:
1. To overcome the lower treatment capacity of digester in batch test, research was mainly focused on the semi-continuous AD. The optimumoperation codition and the model for predicting methane production insemi-continuous AD were investigated. Results of batch test indicated that theoptimum TS for AD was5.6%, corresponding to the biogas production of888mL/g-VS. The optimum operation condition for semi-continuous AD was:8g-VS/L organic load and2d retention time. At this condition, the methaneyield and the corresponding COD of effluent were436mL/g-VS and93.3%,respectively. In a cycle of semi-continuous digestion, biogas productionincluded two models: zero-order model with volatile fatty acids (VFA)accumulation, and one-order model with no VFA accumulation. Moreover,biogas production from AD of each component in FW was also investigated.The biogas production of starch, protein and fat was modeled. Results fromAD of starch indicated that the hydrolysis (rate-limiting) step occurred in theinitial one day. Biogas was mainly produced in day2, and the total biogasproduction was448mL/g-VS. Biogas production of starch matched theslogistic model. By contrast, biogas production of both protein and fatmatched zero-order model. Higher biogas production rate was observed in ADof protein while lower rate was obtained in fat. The whole digestion time forprotein and fat were1day and14days, respectively. Results also showed thatinhibition on biogas production could be caused by fat in co-digestion ofstarch, protein and fat. The actual biogas production was higher than thepredicted data in co-digestion of starch and protein.
2. To avoid the inhibition from both of waste oil and high concentrations ofcationic elements, AD of food waste in a dual solid-liquid (ADSL) systemwas examined in this section. Results from batch test indicated that both ofthe methane production rate and the methane yield in the ADSL system werehigher than that in raw FW (RFW) system. The methane yield of food solidwaste (FSW), food liquid waste (FLW) and RFW were643,659and581mL/g-VS, respectively. In the semi-continuous AD, the optimum organicloading rates (OLR) for FSW, FLW and RFW were9,4and7g-VS/L/d,respectively. The total methane production of RFW and ADSL systems, basedon1kg-VSRFW, were405and460L, respectively, indicating that themethane production increased by13.6%in the ADSL system. The optimumC/N ratio, redistribution of metal element and lower content of waste oil inFSW explain the higher methane production.
3. To further enchance the performance of AD, anaerobic co-digestion ofFW and cattle manure (CM) was investigated. Results of both batch andsemi-continuous tests indicated that the total methane production is enhancedin co-digestion, with an optimum FW/CM ratio of2. At this condition, thetotal methane production in batch test was enhanced by41.1%, and thecorresponding methane yield was388mL/g-VS. Moreover, high suffercapacity was observed in co-digestion system, allowing higher organicloading rate (OLR), e.g.,48g-VS/L, without pH control. In thesemi-continuous digestion, the total methane production in co-digestion, at the OLR of10g-VSFW/L/d, increased by55.2%, corresponding to themethane yield of317mL/g-VS. The C/N ratio and the higher biodegradationof lipids might be the main reasons for the biogas production improvement.
4. To assure AD of FW could be carried out in pilot-scale and even inindustrial-scale, pilot-scale AD was investigated in this section. Experimentswere conducted in20L,30L and300L digesters, respectively. The biogasproduction and methane yield of20L digester were744mL/g-VS and467mL/g-VS, respectively. The corresponding COD of effluent was in the rangeof5g/L-6g/L, and the total nitrogen and sulfide in the effluent were below400mg/L and10mg/L, respectively. Results from30L digester indicated thatthe optimum rotational speed of proper was100r/min. At this condition, themean velocity was0.082m/s. Not only effective mass transfer could beobtained in anaerobic digester but also granular anaerobic sludge could beformed. Analysis showed that the optimum OLR for300L pilot-scale digesterwas6g-VS/L/d. The corresponding biogas production and the COD of theeffluent were680mL/g-VS and4g/L, respectively.
1、由于批式发酵对餐厨垃圾的处理能力较低，本文在批式发酵的基础上，重点考察了序批式厌氧发酵，优化了序批式发酵的操作条件，并建立了序批式发酵过程中一个周期内的甲烷产气模型。批式发酵结果表明，厌氧发酵最佳的总固体（TS）浓度为5.6%，对应的沼气产率可达888mL/g-VS。序批式发酵的最佳进料负荷和保留时间分别为8g-VS/L和2d，对应的甲烷产率和化学需氧量（COD）去除率分别为436mL/g-VS和93.3%。在序批式发酵的一个进料周期内，甲烷的产气规律符合两个模型：有机酸积累时，为零级模型；有机酸无积累时，为一级模型。另外，研究了餐厨垃圾中各主要组分（淀粉、蛋白质和脂肪）单独厌氧发酵时的产气规律，建立了淀粉、蛋白质和脂肪的产气模型。研究结果表明，淀粉单独发酵时，产气规律符合slogistic模型，第1d为水解阶段，为限速步骤，沼气主要在第2d内产生，平均沼气产率为448mL/g-VS。蛋白质和脂肪单独发酵时的产气规律均符合零级模型，蛋白质的代谢速率较快，发酵在1d内完成；而脂肪的代谢速率较慢，发酵需要14d完成。混合发酵时，脂肪对淀粉和蛋白质的降解有抑制作用；在无脂肪存在的条件下，淀粉和蛋白质混合发酵的沼气产率比模型预测值高。
2、为了避免高浓度盐分和油脂对厌氧发酵的影响，研究了双发酵系统处理餐厨垃圾的工艺，即将餐厨垃圾的固液分离分别发酵，同时将油脂去除。批式发酵实验表明，固液分离后的固相和液相的产气速率和甲烷产率均比原餐厨的产气速率高，固相、液相和原餐厨对应的甲烷产率分别为643、659和581mL/g-VS。序批式发酵实验结果表明，固相、液相和原餐厨的最佳负荷率分别为9、4、7g-VS/L/d，在此条件下，固相、液相和原餐厨的甲烷产率分别为540、390、405mL/g-VS。基于1kg-VS原餐厨计，甲烷在双系统和单系统中的总产量分别为405L和460L，这说明甲烷的总产量在固液分离双系统中提高了13.6%。固相中的最佳C/N比、高浓度的微量元素和低浓度的油脂是双系统中沼气产量提高的原因。
3、为了平衡餐厨垃圾中的营养元素，进一步提高厌氧发酵效率，选用了牛粪作为餐厨垃圾的混合物，考察了餐厨垃圾与牛粪混合发酵性能。批式实验结果表明，当餐厨垃圾与牛粪的比例（FW/CM）为2：1时，厌氧发酵的甲烷产率最高，此配比下的批式发酵实验中，餐厨垃圾负荷为8g-VS/L时，混合发酵比餐厨垃圾单独发酵时的甲烷产率提高了41.1%，对应的甲烷的产率为388mL/g-VS。牛粪的加入提高了系统的缓冲能力，在没有pH调控的情况下，厌氧发酵能够在48g-VS/L的高负荷下稳定运行。利用响应面技术对甲烷产率进行了优化分析，结果表明，当餐厨垃圾的负荷为10g-VS/L/d时，混合体系的甲烷产率提高了55.2%，对应的甲烷产率为317mL/g-VS。较适宜的C/N、牛粪中丰富的微量元素和更强的油脂去除能力是混合发酵中沼气和甲烷产量提高的主要原因。
4、为了进一步提高厌氧发酵水平，本文对厌氧发酵罐进行了放大，分别考察了20L、30L和300L发酵罐的厌氧发酵。发酵稳定时，20L发酵罐的沼气和甲烷的产率分别为744mL/g-VS和467mL/g-VS，对应废水的COD值在5-6g/L之间，总氮和总硫的含量分别在400mg/L和10mg/L以下。30L发酵罐序批式发酵时的最佳的搅拌转速为100r/min，在此转速下发酵罐内部的大部分发酵液处于流动状态，平均流速为0.082m/s，既可以形成有效的传质，又可以形成致密性较好的颗粒污泥。300L发酵罐最佳的餐厨垃圾负荷为6g-VS/L/d，对应的平均沼气产率和废水COD分别为680mL/g-VS和4g/L。
The discharge of food waste (FW) is increasing due to the populationgrowth of the world. Large amount of FW, on the one hand, has caused severeenvironmental pollution in many countries. On the other hand, lots ofbio-energy in FW was wasted. The traditional disposal methods (e.g., aniamalfeed, incineration and landfill) could not meet the current demand ofenvironmental protection. As a green process, anaerobic digestion (AD) couldnot only dispose large amount of FW effectively, but also transform thebio-energy in organic waste into biogas. Biogas production from AD of FWwas investigated in this present paper. Pilot-scale anaerobic digestion wascarried out based on the operation condition of lab-scale anaerobic digestion.Anaerobic digestion in a dual solid-liquid (ADSL) system was applied toovercome the inhibition from higher concentration of salts and lipids.Moreover, to balance the nutrient elements of FW and enhance AD efficiency,cattle manure (CM) was applied as a co-substrate for AD of food waste. Themain contents are as follows:
1. To overcome the lower treatment capacity of digester in batch test, research was mainly focused on the semi-continuous AD. The optimumoperation codition and the model for predicting methane production insemi-continuous AD were investigated. Results of batch test indicated that theoptimum TS for AD was5.6%, corresponding to the biogas production of888mL/g-VS. The optimum operation condition for semi-continuous AD was:8g-VS/L organic load and2d retention time. At this condition, the methaneyield and the corresponding COD of effluent were436mL/g-VS and93.3%,respectively. In a cycle of semi-continuous digestion, biogas productionincluded two models: zero-order model with volatile fatty acids (VFA)accumulation, and one-order model with no VFA accumulation. Moreover,biogas production from AD of each component in FW was also investigated.The biogas production of starch, protein and fat was modeled. Results fromAD of starch indicated that the hydrolysis (rate-limiting) step occurred in theinitial one day. Biogas was mainly produced in day2, and the total biogasproduction was448mL/g-VS. Biogas production of starch matched theslogistic model. By contrast, biogas production of both protein and fatmatched zero-order model. Higher biogas production rate was observed in ADof protein while lower rate was obtained in fat. The whole digestion time forprotein and fat were1day and14days, respectively. Results also showed thatinhibition on biogas production could be caused by fat in co-digestion ofstarch, protein and fat. The actual biogas production was higher than thepredicted data in co-digestion of starch and protein.
2. To avoid the inhibition from both of waste oil and high concentrations ofcationic elements, AD of food waste in a dual solid-liquid (ADSL) systemwas examined in this section. Results from batch test indicated that both ofthe methane production rate and the methane yield in the ADSL system werehigher than that in raw FW (RFW) system. The methane yield of food solidwaste (FSW), food liquid waste (FLW) and RFW were643,659and581mL/g-VS, respectively. In the semi-continuous AD, the optimum organicloading rates (OLR) for FSW, FLW and RFW were9,4and7g-VS/L/d,respectively. The total methane production of RFW and ADSL systems, basedon1kg-VSRFW, were405and460L, respectively, indicating that themethane production increased by13.6%in the ADSL system. The optimumC/N ratio, redistribution of metal element and lower content of waste oil inFSW explain the higher methane production.
3. To further enchance the performance of AD, anaerobic co-digestion ofFW and cattle manure (CM) was investigated. Results of both batch andsemi-continuous tests indicated that the total methane production is enhancedin co-digestion, with an optimum FW/CM ratio of2. At this condition, thetotal methane production in batch test was enhanced by41.1%, and thecorresponding methane yield was388mL/g-VS. Moreover, high suffercapacity was observed in co-digestion system, allowing higher organicloading rate (OLR), e.g.,48g-VS/L, without pH control. In thesemi-continuous digestion, the total methane production in co-digestion, at the OLR of10g-VSFW/L/d, increased by55.2%, corresponding to themethane yield of317mL/g-VS. The C/N ratio and the higher biodegradationof lipids might be the main reasons for the biogas production improvement.
4. To assure AD of FW could be carried out in pilot-scale and even inindustrial-scale, pilot-scale AD was investigated in this section. Experimentswere conducted in20L,30L and300L digesters, respectively. The biogasproduction and methane yield of20L digester were744mL/g-VS and467mL/g-VS, respectively. The corresponding COD of effluent was in the rangeof5g/L-6g/L, and the total nitrogen and sulfide in the effluent were below400mg/L and10mg/L, respectively. Results from30L digester indicated thatthe optimum rotational speed of proper was100r/min. At this condition, themean velocity was0.082m/s. Not only effective mass transfer could beobtained in anaerobic digester but also granular anaerobic sludge could beformed. Analysis showed that the optimum OLR for300L pilot-scale digesterwas6g-VS/L/d. The corresponding biogas production and the COD of theeffluent were680mL/g-VS and4g/L, respectively.
引文
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